Pesticidal compositions and methods



lf tfa l isia stetetasa 7,K aw /a W iii? United This is a division of mycopending application S.N. 143,539, filed October 9, 1961.

This invention describes certain novel biocidal tricyclic sultones andmethods for their use and preparation.

More particularly, this invention relates to hexahalo tri-unsaturatedtricyclic sultones having utility as pesticides, particularly as fungicides and miticides, as pesticidal intermediates and asusefuhcherfiical lfifeimediates generally. These compositions have thestructure:

wherein X is a member of the group consisting of the halogens. The Xsubstituents may be the same or different halogens.

The compounds having preferably all chlorine or all bromine substitutedon the left hand bicyclic moiety are the preferred compositions of thisinvention because of ease of synthesis, the availability of startingmaterials and the cost of manufacture. For the sake of brevity, thehexachloro composition of this invention is referred to as C H O Cl S.

The hexahalo compositions of this invention are crystalline solidshaving sharp melting points. The hexachloro product is a colorlesscrystalline solid of MP. 130 degrees centigrade. This chlorinatedproduct is stable up to temperatures of about 230 degrees centigrade atwhich temperature it breaks down with evolution of It is substantiallyinsoluble in water and is soluble in most organic solvents includingaromatic hydrocarbons such as xylene, chlorinated hydrocarbons,alcohols, ketones, esters, and ethers, and slightly soluble in alkanes.

As indicated above, the compositions of this invention exhibitpesticidal activity, and are particularly outstanding as fungicides.They also possess certain insecticidal activity such as toxicity towardmites and the like, and are active also against bacteria and marinefouling organisms. In addition, the compositions of this invention,their halogenation products, thermal decomposition products,hydrogenation products, adducts and products in which the sultone ringhas been cleared or opened by nucleophilic reagents are useful aspesticides, as intermediates for preparing pesticides, or for organicsynthesis generally.

In addition to their major advantages of biocidal activity and theiravailability as biocidal intermediates and chemical intermediates, thisinvention in its composition aspect offers other additional majoradvantages.

For example, these compositions due to their unique structure, stabilityand solubility in a variety of organic solvents lend themselves toformulation in diverse forms ranging from the simple to the complex. Theinvention compositions may be utilized as biocides, particularly asfungicides and miticides in the pure form or as reaction crudes. Wherethey are to be used as intermediates, the purified product is often bothnecessary and desirable.

The pesticidal preparations are conveniently made up as liquid or assolid formulations. Examples of solid formulations are dusts, wettablepowders, granules and taE 3,218,230 atented Nov. 16, 1965 inventioncompositions combined with a solid carrier or extender, ordinarily anon-reacting or inert substance such as sand, clays, tales, sawdust,flours, alkaline earth carbonates, oxides, phosphates, and the like aswell as diatomaceous earths, micas and similar suitable materials.

Where liquid formulations are desirable, liquid extenders, diluents orcarriers of a non-reactive nature are utilized. Examples of suchmaterials are aliphatic alcohols, chlorocairbons, ketones and glycols,aromatic hydrocarbons, petroleum fractions and distillates among manyothers.

Where it is desired to use the aforementioned wettable powders, orliquid formulations either emulsified, dispersed or suspended in wateror other fluid, one or more of a class of materials herein referred toas adjuvants may be incorporated into the powder, dust, or liquidformulation. These materials comprise surface active agents, detergents,wetting agents, solubilizing agents, stabilizers, dispersing agents,suspending agents, emulsifying agents, spreaders, stickers, andconditioning agents generally. These materials through their modifyingcharacteristics facilitate handling and application, and notinfrequently enhance or potentiate the compositions of this invention intheir pesticidal activity by mechanisms frequently not well understood.

A satisfactory but not exhaustive list of these substances appears amongother places in Soap and Chemical Specialties, volume 31, No. 7, page61; No. 8, pages 4861; No. 9, pages 52-67, and No. 10, pages 38-67(1955) Also, see Bulletin E-607 of the Bureau of Entomology and PlantQuarantine of the United States Department of Agriculture.

An additional advantage of the inventive compositions is theircompatibility with a variety of biocidal materials. For example, it mayfrequently be convenient to combine one or more compositions of thisinvention with one or more adjuvants and carriers with insecticidalmaterials such as chlordane, benzene hexachlorides, QDI DDJL theinsecticidal carbamates, polychlorinated terpenes, the parathions,methoxychlor, insecticidal phosphates, phosphorothioates, andphosphorodithioates, with other fungicides such as sulfur, quinones,dodecylguanidine, the metal dimethyldithiocarbamates,N-trihalomethylthio-4- cyclohexene-1,2-dicarboximide,N-(trichlorome-thylthio) phthalimide, heptadecylimidazoline,dinitrocapryl crotomate and various fungicidal zinc, iron, nickel,manganese, copper, lead and mercury salts.

In its process aspects, the present invention offers several otheradvantages in addition to making available a source of biocidally activematerials. For example, these processes offer two separate and distinctnovel routes to the synthesis of the cyclic dienic six-membered ring sultones of this invention. Heretofore, only one prior art process wasavailable to prepare six-membered dienic sultone rings. For example, thestructure where A, B, D and E (which may be the same or different) areselected from the group consisting of hydrogen and alkyl, have beenprepared hitherto only by the reaction of unsaturated ketones withsulfuric acid in the presence of acetic anhydride. However, the priorart process would appear to be limited to the preparation of thosesultones having an alkyl group on the carbon atom adjacent to the ringoxygen. Furthermore, the prior art process is severely limited incommercial applicability by the general commercial unavailability of11,}3- or pa -unsaturated ketones, with only a few exceptions. Anothershortcoming pellets. Each of these may contain one or more of the of theprior art process is the necessity of employing acetic anhydride, whichadds expense without adding any moiety to the end product.

Specifically in regard to the present inventive compounds, the prior artprocess is inapplicable because of all of these factors.

Unexpectedly, it has been discovered that six-membered dienic sultonerings can be prepared by a number of novel and distinct, but related,processes.

The new processes of the invention comprise the reaction of at least onecompound of the group consisting of compounds of the formula andcompounds of the formula I OHY where A, B, C and D (which may be thesame or different) are selected from the group consisting of hydrogen,halogen and alkyl (and where two or more are alkyl, said alkyls beingoptionally conjoined to form a ring), where G is selected from the groupconsisting of hydrogen and halogen, and where Y and Z (which may be thesame or different) are chosen from the group consisting of halogen,hydroxy, and acyloxy, said compound being reacted with a reagent chosenfrom the group consisting of concentrated sulfur acid, oleum, andsulfuric anhydride, said reaction being conducted by admixture at about----20 to 150 degrees centigrade.

The present invention consists in its process aspect of the reaction ofat least one compound chosen from the group described by the generalformula 1 01 o1 {W=orro1 01 onzorr 001, 001, o1 l =OH, o1 omorr c1 c1 01=o11, 01 -ornooona icon oonl 01 (L =o1r, 01 L CHzOOOCHs 01 l ornoi or 1}0mm The above being preferred because of greater commercial In regard tothe sulfur-containing reagent, oleum (i.e. sulfuric acid containing freeS0 is preferred. Also usable are sulfuric acid, sulfuric acid plus adehydration agent such as P 0 or sulfuric anhydride, or complexes ofsulfuric anhydride with various Lewis bases such as dioxane, ethylether, pyridine, or the like.

The above reactions are carried out in the liquid phase by admixing oneor more of the reactants with the sulfonating reagent present in molarexcess at temperatures ranging from about 20 degrees centigrade to +150degrees centigrade, preferable Zero degrees centigrade to degreescentigrade. The reaction is operable though sluggish at the lowertemperature range while at temperatures toward degrees centigrade andabove there is some tendency for undesired and competing side reactionsincluding sulfonation and/or oxidation of the product. The preciseoptimum operating temperature is largely dependent upon the reactivityof the particular aliphatic reactant used. The time will normally be afew minutes to several hours. Isolation of the sultone product may bemade through a variety of means including precipitating the productthrough adding the reaction mixture to water, or by extraction with asulfuric acidstable organic solvent, followed by evaporation and crystallization, or by freezing the crystals out. A most convenientisolation procedure is dilution with water, followed by filtration ofthe crude product or extraction of the precipitated crude product bymeans of a solvent.

In respect to pesticidal use, the preferred method of employing thenovel sultones of this invention is to apply the compounds or aformulation thereof to the site of the crop to be protected or to thesoil, seeds, roots, foliage, branches or fruit. While the precise ratesof application depend upon the type and degree of infestation and thetolerance of the plant and the part of the plant treated, rates of from0.1 to 10 pounds per acre will generally be suitable in foliarapplication, lower rates in seed application down to 1 ounce per acre,with higher rates, up to and above 100 pounds per acre in soilapplication. While the emphasis in this application has been primarilythat of fungicidal treatment of plants, the compounds of this inventionused serve equally well as an antimicrobial agent in wood, paper, cloth,leather, stored food products, pulp, plastics and other substancessuitable to deterioration due to microorganisms, and will generally beused at 0.1 p.p.m. or higher, in the medium to be treated. The compoundsalso have utility in paints, varnishes, and other coatings forprevention of attack by fungi, mildew, marine fouling organisms, and thelike.

The following additional examples are submitted to more clearlyillustrate the workings of this invention. Except as indicated in theclaims, none of the submitted exemplification is to be construed aslimitations of this invention in its composition and process aspects.

Example 1.Preparation of C H Cl S sultone from1,4,5,6,7,7-hexachlor0-2,3-b'is(chloromethyl)bicyclo(2.-2.1)-heptadiene-2,5

A mixture of 20 parts of 1,2,3,4,7,7-hexachloro-5,6-bis-(chloromethyl)bicyclo(2.2.1)-heptadiene-2,5 (prepared as in UnitedStates Patent 2,951,098) and 75 parts of oleum (20% S0 content) iswarmed at 75 degrees centigrade for one-half hour. The resultant clearsolution is poured with agitation into water at zero to 10 degreescentigrade (approximately 1000 parts). The precipitated solid is removedby filtration and, after washing with water to remove adhering acid, anddrying, the solid is recrystallized from hot heptene to obtain 18 partsof colorless crystalline solid, melting point 130 degrees centigrade.

Analysis.-Calcd. for C H O Cl S: C, 26.9; H, 0.50; Cl, 52.9; S, 7.94.Found: C, 26.84; H, 0.55; Cl, 52.8; S, 7.99.

The infrared spectrum provides evidence for the OSO group as well as twovinylic hydrogen-tocarbon bonds (=CH structures) Molecular weight calcd.405; found (ebullioscopic in benzene), 388 (i10% Example 2.Preparati0nof C H O Cl S sultone from 1,4,5,6,7,7-hexachl0ro-2,3bis(methylene)bicyclo(2.2.- 1 -heptene- Example 3.-Preparation of C H OCl S sultone from 1,4,5,6,7,7-hexachl0r0-2,3 bis(hydroxymethyl) bicyclo-(2.2.1 -heptadiene-2,5

A mixture of parts of 1,4,5 ,6,7,7-hexachloro-2,3-bis-(hydroxymethyl)bicyclo(2.2.1)-heptadiene-2,5 (J. Am. Chem. Soc. 81,5416) and 75 parts of oleum (20% S0 are stirred together, causing anexotherm to 50 degrees centigrade. After 3 hours, the product isisolated and recrystallized as in Example 1, to obtain 5 parts of aproduct which is the same as in the above examples, by melting point andinfrared spectrum.

Example 4.Preparati0n of C H 0 Cl S sultone from1,4,5,6,7,7-hexachl0r0-2,3 bis(acet0xymethyl) bicyclo- (2.2.1-heptadiene-2,5

A mixture of 100 parts of 1,4,5,6,7,7-hexachloro-2,3-bis(acetoxymethyl)bicyclo(2.2.1)-heptadiene-2,5 (J. Am. Chem. Soc. 81,5416) and 500 parts of oleum (20% S0 is heated for 5 hours at 70 degreescentigrade and the product isolated as above and found to be the samecompound C H O Cl S by infrared spectrum and melting point. By stoppingthe reaction after a one-hour period, 1,4,5,6,7,7-hexachloro-2hydroxymethyl-3-acetoxymethylbicyclo(2.2.1)-heptadiene is isolated andcharacterized by infrared spectrum, indicating this to be a reactionintermediate capable of yielding the sultone by further reaction witholeum.

Example 5 .Preparation of C H 0 Cl S sultone from hexachloro-Z-methylene3 (chloromethylene)-bicycl0 (2.2.1)heplene-5 A mixture of 5 parts of1,4,5,6,7,7-hexachloro-2-methylene-3-(chloromethylene)-bicyclo(2.2.1)-heptene-5 (prepared bydehydrochlorination of 1,4,5,6,7,7-hexachloro- 2,3bis(chloromethyDbicyclo(2.2.1) heptadiene-2,5 by KOH in CH OH at reflux)plus 12.5 parts of oleum (20% S0 was heated for 30 minutes at degreescentigrade, then the product isolated and purified as in Example 1,giving a nearly quantitative yield of the sultone C H O Cl S, identicalin melting point and infrared spectrum to that made in Example 1.

Example 6.Use of 65% oleum Twenty parts of1,4,5,6,7,7-hexachloro-2,3-bis(chlorornethyl)bicyclo(2.2.1)-heptadieneand 80 parts of oleum (65% S0 were mixed at room temperature, causing anexotherm to 60 degrees centigrade. When the exotherm subsided, thesolution was poured slowly into water, and the product isolated byextraction using chloroform, the chloroform evaporated, and the crudeproduct purified as in the preceding examples, to obtain 12 parts of thesultone C H C1 SO identified by melting point and infrared spectrum.

Example 7.Use of sulfuric anhydria'e Twenty parts of1,4,5,6,7,7-hexachloro-2,3-bis(chloromethy1)bicyclo(2.2.1)-heptadiene-2,5was dissolved in 75 parts of liquid sulfur trioxide (commercialstabilized Sulfan), with cooling to hold the temperature below 50degrees centigrade. After 10 minutes, the solution was cautiously addedto crushed ice, and the product extracted from the aqueous-organicmixture by means of chloroform. On evaporation of the chloroform, asyrup was obtained which, on dissolving in heptane and chilling theresultant solution, yielded 7 parts of the crystalline sultone C H Cl SOidentified by infrared spectrum and melting point.

Example 8.-Use of sulfuric acid Three parts of1,4,5,6,7,7-hexachloro-2-methylene-3-(chloromethylene)bicyclo(2.2.1)-heptene-5 and thirtyfive parts ofessentially pure sulfuric acid (made by adding sulfuric anhydride in anamount equivalent to the water present in technical ninety-six percentsulfuric acid), are heated at seventy degrees for one hour, then pouredinto water. The precipitated solids are filtered off and found to be thesultone C I-I O Cl S by infrared analysis.

Example 9.Emulsifiable formulation An emulsifiable formulation of thecompound (prepared as above) is made by blending the followingingredients:

Parts C H O Cl S 1.0 Emcol SOOX (commercial polyoxyethylenesulfonateemulsifier) 0.3 Emcol 300X (commercial polyoxyethylenesulfonateemulsifier) 0.3 Xylene 6.4 Isophorone 2.0

This formulation is emulsified with water prior to spraying.

Example 10.Dust formulation A dust formulation of C H O Cl S is made bygrinding together the following:

Parts Attapulgus clay 95 C9H203C16S 5 This formulation is applied tocrops from a dusting apparatus.

Example ]1.--Wettable powder A wettable powder formulation of C H O Cl Sis made by grinding together the following materials:

Part C H O Cl S 1 Microcel E (synthetic silicate) 0.90 Marasperse N(lignin sulfonate dispersant) 0.05 Sorbit P (alkylarylsulfonate wettingagent) 0.05

This formulation is dispersed in water prior to spraying.

Example 12.--Fungicidal use Twenty tomato plants infested with spores ofAlternaria solani (early blight disease) are sprayed with wettablepowder dispersions of C H O Cl S (as prepared above). Twenty infestedplants are left unsprayed. Two weeks later when the untreated plants haddeveloped numerous leaf lesions due to the disease, the lesions on thesprayed plants were counted and the percent repression of leaf lesionsrelative to the unsprayed controls was calculated (as percent control).The results are as follows:

Concentration of C H O Cl S: Percent control 100 p.p.m 100 50 p.p.m 100p.p.m. 98 12.5 p.p.m. 80

Example 13.Fungicidal use Similar tests to the above were run usingtomato plants infested with Phytophthora infestans, the causativeorganism of late blight disease. The following percentages of controlwere observed:

Concentration of C H O Cl S: Percent control 100 p.p.m 100 50 p.p.m. 9925 p.p.m. 94

Example J4.Fungz'cidal use Spore germination tests are carried out bythe standard method of the American Phytopathological Society, employingAlternaria oleracia and Monolinia fru'cticola as test organisms. Maneb(manganous ethylenebis(dithiocarbamate) a highly effective commercialfungicide,

was tested for comparison. The results are as follows:

Percent Germination of Spores at Concentrations (p.p.m.) IndicatedCompound Fungus CnHgOgClqS CnHzOaClaS Maueb Example 15.-Miticidalactivity the structure:

OH L a X l/\ X or:

wherein X is halogen plus at least one adjuvant chosen from the groupconsisting of a solvent, a surface-active agent, an emulsifying agent, adispersing agent, a solid carrier and a liquid carrier.

2. A method of controlling microorganisms comprising the application ofa fungicidal amount of a compound of the structure:

X CH tr X I X on wherein X is halogen, to the locus of the microorganismto he treated.

3. A method of controlling mites comprising the application to the mitesof a miticidal amount of a compound of the structure:

l o it to X 2 X ofi wherein X is halogen.

References Cited by the Examiner UNITED STATES PATENTS 11/1958 Gilbert16733 8/ 1959 Broderick 260327 11/1960 Bimber 167-33 5/1961 Geering eta1. 260'327 2/ 1963 Geering 260-327 OTHER REFERENCES Mustafa: Chem.Reviews, vol. 54, #2, pages -197 (1954).

JULIAN S. LEVITT, Primary Examiner.

1. A PESTICIDAL COMPOSITION COMPRISING AS A PRINCIPAL ACTIVE INGREDIENTA PESTICIDAL AMOUNT OF A COMPOUND OF THE STRUCTURE: